Polyester fibers dyed with methylidynebis pyrazolone dyestuffs

ABSTRACT

WHEREIN EACH OF R1, R2 and R3 is independently hydrogen, lower alkyl, chloro, bromo or lower alkoxy; ONE Y is hydrogen and the other Y is   D R A W I N G GROUP FORM A HETEROCYCLIC GROUP HAVING FIVE OR SIX RING ATOMS.   EACH R4 is independently lower alkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(lower alkyl), phenyl, chlorophenyl, bromophenyl, lower alkylphenyl, cyano(lower alkyl)phenyl, nitrophenyl, sulfamylphenyl, N,N-di(lower alkyl)sulfamylphenyl, N-(lower alkyl)sulfamylphenyl, lower alkylsulfonylphenyl, cyanophenyl, di(lower alkyl) carbamylphenyl or lower alkoxyphenyl; or THE TWO R4 groups taken together with the adjacent   Dyestuffs for polyester and plastic substrates are provided by reacting a methylidynebis pyrazolone with an N-methylolamide. The dyestuffs have the formula

United States Patent [191 Renfrew POLYESTER FIBERS DYED WITH METHYLIDYNEBIS PYRAZOLONE DYESTUFFS [75] lnventor: Edgar Earl Renfrew, Lock Haven,

' I Pa.

[73] Assignee: American Aniline Products, Inc., Paterson, NJ.

221 Filed: Mar. 10, 1972 21 AppL N01: 233,707

[52] US. Cl. 8/179, 260/240 R, 260/240 F, 260/240.1 [51] Int. Cl D06p 3/54 [58] Field of Search 8/179; 260/240 R, 260/2401, 240 F [56] References Cited UNITED STATES PATENTS 2,840,443 6/1958 Smith 8/173 2,903,451 9/1959 SmithJ... 260/240 R 2,903,452 9/1959 Smith 260/240 F Primary ExaminerLeon D. Rosdol Assistant Examiner-T. .1. Herbert, Jr. Att0rney-Armstrong & Wegner [57 1 ABSTRACT Dyestuffs for polyester and plastic substrates are provided by reacting a methylidynebis pyrazolone with an N-methylo1amide.' The dyestuffs have the formula 1 1 CH CH:

wherein each of R R and R is independently hydrogen, lower alkyl, chloro, bromo or lower alkoxy;

'- alkyl),

v [111 3,785,769 [451 Jan. 15, 1974 one .Y is hydrogen and the other Y is 3 Claims, No Drawings POLYESTER FIBERS bYEnwr'rn METHYLIDYNEBIS PYRAZOLONE DYESTUFFS BACKGROUND pm: INVENTION Manycompounds have'been proposed over the years as dyes for synthetic fibers. With the emergence of the relatively newer synthetic fibers, such aspolyethylene terephthalate, the search for dyes which are capable of coloring such newer synthetics has increased. Although much exploration has taken place in the am and anthraquinone areas, comparatively little research has been conducted 'in the area of methylidynebis pyrazolones; Although Smith, inliLS.- Pat. No. 2,840,443, reports certain methylidynebis pyrazolones, there has been1a lack of successful research repor-ted for more than a decade on relatedcompounds.

SUMMARY or rne INVENTION,

According to a first aspect of the invention there are provided yellow polyester fabrics, wherein the yellow coloration of the polyester is attained through the dyeing of the polyester with anovel class of-methylidynebis pyrazolone's.

According to a second aspect of the inventionthere are provided plastic materials' having a yellow coloreach R is independentlylower alkyl, chloro(lower alkyl), bromo(lower alkyl), cyano(lower alkyl),

phenyl, chlorophenyl, bromophenyl, lower alkylphenyl, cyano(lower alkyl)phenyl, nitrophenyl, sulfamylphenyl, N,N-di(lower alkyl) sulfamylphenyl, N-(lower alkyl)sulfamylphenyLlower alkylsulfonylphenyl, cyanophenyl, di(lower alkyl)carbamylphenyl or lower alkoxyphenyl; or

i the two R groups taken together with the adjacent group form a heterocyclic group having five or six ring ation, wherein the yellow coloration is'achieved" with Y the inclusion of a novel methylidynebis pyrazolone;

According to a third aspect of the'inve'ntion thereis provided a novel class of dyestuffs of the formula wherein each of R R and R is independently hydrogen,

lower alkyl, chloro,vbromo or lower alltoxy; one Y is hydrogen and the other. Y is atoms.

DETAILED 'DESCRIPTION The compounds of the invention (1) are produced via the reaction of an intermediate methylidynebis pyrazolone of the formula VVVVV W U H: AH:

wherein R R and R areas defined above, with an N- 'methylol compound HO--Y (lll) phthalimide on heating in water with an excess of paraformaldehyde yields N-hydroxymethylphthalimide in excellent yields. In the preparation of N- hydroxymethylamides, the reaction is often speeded by the addition of an alkali such as potassium carbonate.

Synthesis of the compounds of the invention may conveniently be carried out in accordance with the following procedure. lnto 96 percent sulfuric acid at room temperature is added the intermediate methylidynebis pyrazolone (II). The N-methylol compound (III) is added, incrementally thereto with external cooling to maintain the temperature below about'2lC. The reaction is allowed to continue with stirring, maintaining the temperature below about 25C.

According to a preferred embodiment there are provided compounds of the invention Y is a group of the formula COR,

-CHzN wherein the two R, groups together form a heterocyclic ring with the adjacent N(CO) group. Preferred embodiments include: (1) ortho-arylene groups such as ortho-phenylene and its chloro, bromo, carbamyl and sulfamyl-substituted forms; (2) lower aliphatic groups of two to six carbon atoms containing two or three carbon atoms between the carbonyl groups which may be substituted by chloro, bromo or cyano. Examples are As used herein with reference to aliphatic moieties, the term lower constitutes the recognized lower members of the series, preferably containing not greater than six carbon atoms in a linear or branched aliphatic chain. For example, with reference to lower alkyl may be mentioned the groups methyl, ethyl, npropyl, isopropyl, n-butyl, sec-butyl, tert-butyl and nhexyl. According to a preferred embodiment, the lower aliphatic groups contain from one to four carbon atoms.

To prepare the product for application to the polyester substrates the product must be suitably dispersed. This may be done in any of several well-known methods, milling as in a ball-mill with dispersing agents such as lignin sulfonic acid materials, for instance. The resultant aqueous dispersion can be dried, as in a spraydryer, or preserved and used as a paste. Standardization to any desired lower strength can be done with inert colorless diluents such as inorganic salts for powders, or water for pastes. Other materials such as preservatives, foam-control agents, and wetting agents may be added as desired.

Dispersed pastes are made by wet milling the dye in conventional equipment in the presence of a dispersing agent, preferably sodium lignin sulfonate or sodium alkyl-naphthalene sulfonate. Various other commercially available dispersing agents, such as sodium salts of carboxylated polyelectrolytes and the naphthalene sulfonates; e.g., the condensation products of sulfonated naphthalene and formaldehyde, such as sodium dinaphthylmethane disulfonate, are conveniently used.

The oil disperse paste may be cut or standardized to a standard strength with water. The final colorcontent of I the finished paste averages from l0-40 percent by product when it is placed in the dye bath. Disperse powders are usually cut or standardized to 25-60 percent by weight color content (pure color).

The dye is preferably applied to the aromatic polyester fiber by thermofixation methods, such as the Thermosol process. This process involves padding the cloth with a dilute dye dispersion, followed by drying to remove water (e.g., by preheating with infrared heat) and curing by dry heat fixation using dried hot air or heated contact rolls. Curing or fixation temperatures of 350-430F are used for less than 2 minutes, usually for 30 to seconds. Ordinarily, if the padded fabric is entirely polyester, curing is done at 400430F. If the fabric contains cotton or viscose rayon, apart from synthetic fibers, there is little danger of damaging cellulosic portions, but if wool is present, the curing temperature must be kept below 357F and the time must be reduced to about 30 seconds.

For durable press finishing of mixed polyester-cotton blends, after thermofixation the residual unfixed dye is removed from the fabric by scouring and the cleaned fabric is given a durable press cure at 300350F. The

new dyes of the invention show an excellent diffusion rate in the polyester fibers at the dyeing temperature and a low diffusion rate at the preferred press curing temperature of 300350F.

The compounds of the invention may be used for the coloration of rigid plastic substrates. The rigid plastic substrates contemplated within the scope of the invention are those plastic materials capable of being pigmented with the compounds of the invention, and will be referred to herein as rigid plastic substrates. The rigid plastic substrates of the invention include those materials capable of being formed into a shaped article, including semi-rigid materials which may be deformed by application of pressure.

As rigid plastic substrates of the invention may be mentioned terpolymers, including acrylonitrilestyrene-butadiene, often known as ABS; acrylics, including methacrylics; polystyrene, both foamed and rubber modified polysulfones; cellulosie derivatives, particularly esters such as cellulose acetate, propionate and butyrate; polyamides such as nylon; epoxy and phenolic resins; polycarbonates; and polyesters. It is understood that the rigid plastic substrates include those materials capable of being pigmented with the compounds of the invention, and therefore copolymers of the above classes of compounds, such as styrenebutadiene, are also within the scope of the invention.

Specific examples of thermoplastic resins include polyvinyl chloride, polyvinyl acetate, vinyl chloridelacetate copolymers, polyvinyl alcohol, polyvinyl acetal, ethylene/vinyl acetate, ethylene/vinyl propionate, ethylene/vinyl isobutyrate, ethylene/vinyl alcohol, ethylene/methyl acrylate, ethylene/ethyl acrylate ethylene/ethyl methacrylate, ethylene/ally] alcohol,

ethylene/ally] acetate, ethylene/ally] acetone, ethylenelallyl benzene, ethylene/allyl ether, ethylene/acrolein, polyhexamethylene adipamide, polyhexamethylene sebacamide, polycaprolactam, polymethyl methacrylate, polyacrylonitrile, polymethyl acrylate, polyethyl After the compounds and the plastic have been thoroughly mixed, the resultant colored mixture is shaped into the desired final form through procedures well known to those skilled in the art, such as pouring, calendering, extrusion, spreading, or injection molding. Where the desired product is a semi-rigid material, plasticizers may advantageously be added prior to shaping into the desired final form. As plasticizers suitable for this purpose may be mentioned esters of phthalic acid. Although the plasticizer may be incorpo rated after the mixing of the compound of the invention with the rigid plastic substrate, it also can be incorporated into the rigid plastic material prior to mixing the pigment with the rigid plastic material. In order to vary the strength of the finished product or vary the color, it is also possible to add additional pigments or fillers in an amount sufficient to obtain the desired effect.

The amount of the compound ofthe invention which is used to color the rigid plastic substrate may vary widely depending upon the degree of color wished to be imparted to the final product, and depending upon whether the compound of the invention is the sole colorant or whether it is used in admixture with other plastic colorants. When the compound of the invention is used in admixture with other colorants, obviouslya very minute quantity may be used to produce a complementary effect. Generally, the amount of colorant comprises less than l5 percent, preferably less than about 8 percent, by weight in relation to the rigid plastic substrate. An amount of colorant compound which has proved particularly valuable is about 0.0001 percent to about 1 percent. 7

The following examples serve to further illustrate the invention (the Y group in each example is attached to a phenyl nucleus):

A 500ml. three-necked flask is fitted with a stirrer, a thermometer, and a temperature controllingbathand is charged with 359 g. sulfuric acid, 96percent. To this is added in small portions at l92lC, 35.9 g. 4.4- methylidynebis-3-methyl-l -phenylpyrazolidine-5-one, the temperature being maintained by slight external cooling. After one hour, there is added 18.7 g. N- hydroxy-methylphthalimide in small portions, with sufficient external cooling to maintain the internal temperature below 21C. After the addition has been completed, the mixture is stirred for sixteen hours, during which time the temperature is allowed to rise to that of the surrounding, 25C.

The mixture is drowned into 1,000 ml. ice water. The temperature is kept below 5C by adding ice as needed.

EXAMPLE ii To a ball mill is charged 50 g. of the product of Example l, 25 parts of a commercially available ligninsulfonic acid salt marketed as a dispersing agent and 325 g. water. Milling is continued until the dispersion is satisfactory as shown by filter tests.

The disperse paste is applied to polyethylene terephthalate fabric by established dyeing methods (thermofix, carrier and pressure) and the dyed goods are subjected to the textile fabric tests developed and published by the American Association of Textile Chemists and Colorists. The dyed fabric isbright greenish-yellow in hue; the dyeing shows outstanding sublimation resistance at 200C and lightand wash-fastness tests show excellent durability.

' EXAMPLE 111 Methyl methacrylate resin is colored with the compound of Example 1 as the colorant, in a ratio of 2 grams resin to 1 mg. colorant. The resin is prepared by placing 1 pound of methyl methacrylate into a Thropp mill (a two-roller mill), which is then heated and run in order to melt and smash the resin to a molten mass. The compound of Example I is added and the entire mixture of resin and colorant is milled until the colorant is uniformly distributed in the mass as measured by eye. While still hot, 30 grams of the hot mass is cut off for use in the following procedure. The sample, containing 30 grams methyl methacrylate and 15 mg. of the compound of Example I as colorant, may be conveniently molded in a Laboratory 40 Single Acting Watson- Stillman Laboratory Press (Farrell-Birmingham Co. SO-ton press). 30 grams of methyl methacrylate mixture containing l5 mg. of the compound of Example l per pound of methyl methacrylate is placed in the cold mold, which is then closed with the Schrader Valve. The drain is opened and steam is applied to the mold. When steam comes through the drain pipe, the drain is closed. Up to 25.0 tons pressure is exerted on the chips until the mold is fully closed. This can conveniently be accomplished by observing the pressure gauge. When the gauge needle no longer decreases in pressure, then The product separates 1n bnght green-yellow flakes.

It is collected on a filter, washed with water and dried.

the mold is closed. I

The mold is held closed at zero pressure by releasing the hydraulic pressure and maintaining the steam for 5 minutes. The mold pressure is increased to 10 tons and held for 10 minutes, the steam remaining on.

The mold pressureis increased to 15. tons and the steam shut off; the drain is opened and cooling water is added for five minutes. Thereafter the pressure is changed to zero and the mold is opened to extract the resultant plastic chip.

EXAMPLE lV 7 EXAMPLE v The compound of Example I may also be used as a colorant to impart a yellow shade to plastics made from polycarbonates. A pigmented plastic material of polycarbonates and the compound of Example 1 may be prepared according to the following procedure;

A specimen is prepared by dry mixing pelletized or powdered resin with finely divided colorant until uniform distribution is achieved of the colorant in the resin material. Plasticizer may also be added, if desired. The mixture is then extruded or injected molded under suitable conditions. 454 gms. Lexan 121R (General Electric) pellets are placed in Bipel one ounce reciprocating screw injection molder. The pellets are tumbled for five minutes on the barrel tumbler. The resin is heated (front zone temperature of 550F and rear zone temperature of 500F) and chips are produced from the virgin resin until chips of good quality are obtained. When the desired quality of chips are obtained with the clear resin, a fresh batch of'Lexan l2l-R, containing the compound of Example I in an equivalent amount corresponding to Example III to produce a pigmented plastic material is fed into the injection molder, to produce yellow pigmented chips.

EXKMFLE vi N-hydroxymethyl-succinimide by the method described in Example I.

The disperse dye so obtained dyes polyethylene terephthalate fabric in bright greenish-yellow shades of excellent fastness properties by following the procedure of Example 11.

EXAMPLE Vlll A compound of the indicated structure is prepared CH: C

EXAMPLE V11 1 1 I T i Q by the method described in Example 1 except that 1 0:) g. 1-hydroxymethyl-2-pyrr0lidinone isused instead of N-hydroxymethylphthalimide.

40 The material, after dispersion yields dyeings similar Ex AMP LEs x xxxrx Yellow dyeings on polyester are obtained from the 45 products of these examples by applying suitably dis- A dye of the indicated structure is prepared from II C-CH:

55 persed dyes by the conventional methods. The sublima- 42.8 g. 4.4-methylidynebis-3-methy1-l(4-chlorotion, lightand wash-fastness of the dyeings of these exphenyl)pyrazolidine-S-one and 12.4 g. amples are excellent.

Example R1 R: R3 Y X... p-Cl H H 0 II C ClIz-N XI p-CHa H H Same as above.

2-01 4-01 H Do. XIII o-OCH; H H Do.

in hue and properties to the product of Example Vll.

Example R1 R2 R; Y

XXXIV H H H CH; C CON\ GHQ-N CH;

XXXV 2-(311; 4-011; H CHz-CH: CH2N I (fi-CH- 0 XXXVI H H H CH:

xxxvn H H H c-o CHzN\ 0-0 XXXVIII H H H t) CCH2\ CHaN /CH2 fi-CH; 0

XXXIX H H H c CHzN 0:0

EXAMPLE XL W Methyl methacrylate, polystyrene and polycarbonate CH1 are colored in yellowish hues when each plastic mate- 4o COR rial is colored with the compounds of Example VI- -XXXlX by using the procedure of Examples ill-V, respectively.

What is claimed is:

l. Polyester dyed with a compound of the formula each of R,, R and R is independently hydrogen,

lower alkyl, chloro, bromo or lower alkoxy; one Y is hydrogen and the other Y is each R is independently lower. alkyl, chloro(lower O 0 R4 )cyano lower alkyl) CH1N I the two R; groups taken toge ihe r with the adjacent and the other Y i s of the fgrrnnla v .cn,N\ (JO-.- -CH1N group form a heterocyclic group having five or six ring atoms. g 2. Polyester of claim I, wherein R}, R and R are hy- 1 drogen r 3. Polyester of claim 2, wherein one Y is hydrogen 

2. Polyester of claim 1, wherein R1, R2 and R3 are hydrogen.
 3. Polyester of claim 2, wherein one Y is hydrogen and the other Y is of the formula 